Chemical composition and gasoline containing same



United States Patent 3,269,811 CHEMICAL COMPOSITION AND GASOLINECONTAINING SAME John H. Udelhofen, Calumet City, 11]., assignor toStandard Oil Company, Chicago, 111., a corporation of Indiana NoDrawing. Original application Apr. 28, 1961, Ser. No. 106,195. Dividedand this application May 22, 1963, Ser. No. 287,456

3 Claims. (Cl. 44-63) This is a division of application Serial No.106,195, now abandoned, filed April 28, 1961, and entitled ChemicalComposition and Gasoline Containing Same.

This invention relates to a chemical composition useful as a corrosioninhibitor in hydrocarbon fuels. This invention further relates tohydrocarbon fuel compositions containing new and useful corrosioninhibitors.

The chemical compositions of this invention are salts of1,2-disubstituted imidazoline and succinamic acid. The salts correspondto the structural formula:

| CHrOH In the formula, R and R each represent an open-chain hydrocarbonradical of 8 to 20 carbon atoms. The hydrocarbon radicals may be asaturated or unsaturated aliphatic radical, having either a straight orbranched chain.

, The salts may conveniently be prepared by reacting equimolar amountsof the 1,2-di'substituted imidazoline and s'uc'cinamic acid. Thereaction proceeds readily at room temperature but the reactants may beheated and agitated if desired to increase the reaction rate. Thereaction is complete When heat of reaction ceases to be evolved. Thereaction is a neutralization reaction with resulting salt formation;such reactions and their conditions, as well as useable catalysts, arewell known to the art.

The succinamic acid and 1,2-disubstituted imidazoline used in the abovereaction may be purchased or may be prepared by methods known in theart. The 1,2- disubstituted imidazolines may be prepared by reaction ofthe corresponding oarboxylic acid (R'COOH) With N-hydroxyethyl ethylenediamine until two moles of water are split out; this occurs upon closureof the imidazoline ring. The succinamic acid may be prepared by reactionof 'equimolar amounts of an amine (RNH with succinic acid under knownconditions to form the amide linkage with the resulting splitting out ofone mole of water.

Illustrative examples of succinamic acid salts of 1,2- disubstitutedimidazolines are 1-(2-hydroxyethyl)-2-heptadecenyl imidazolinium N-tallow succinamate,

1-(2-hydroxyethyl)-2 (2,4-dimethyl hexyl) imidazolinium N-eicosy-l'succinarnate, v

1-(2-hydroxyethyl)-2-palmityl imidazolinium N-caprylyl succinamate, I

I-(Z-hydroxyethyl)-2-lauryl imidazolinium N-lauryl succinamate,

1-(Z-hydroxyethyl)-2-n-octy1 imidazolinium N-n octyl succinamate,

3,269,81 l Patented August 30, 1966 1-(2-hydroxyethyl)-2-n-decenylimidazolinium N-tallow succinamate, I

1-(2-hydroxyethyl)-2-linolenyl imidazolinium N-stearyl succinama'te,

I-(Z-hydroxyethyl)-2-stearyl imidazolinium N-octadeoadienyl succinamate,

I-(Z-hydroxyethyl)-2-nonyl imidazolinium N-capryl succinamate,

1-(2-hydroxyethyl)-2-coco imidazolinium N-co co succinamate,

I-(Z-hydroxyethyl)-2-eicosyl imidazolinium N-eicosyl succinamate,

1-(2-hydroxyethyl)-2-myristy1 imidazolinium N-oleyl succinamate,

l-(2-hydroxyethy1)-2-monohydroxystearyl imidazolinium N-decylsuccinamate,

I-(Z-hydroxyethyl)-2-1inoleyl imidazolinium N-decyl succinamate,

1-(2-hydroxyethyl) -2-soybean imidazolinium N-t-al'low s-uccinamate,

I-(Z-hydroxyethyl)-2-tallow imidazolinium N-tallow succinamate,

1-(2-hydroxyethyl)-2-(3-ethyl hexyl) imidazolinium N-oxooctylsuccinamate, and

1-(2-hydroxyethyl)-2-tallow imidazolinium N-coco succinamate.

The terms coco, soybean and tallow as used herein designate that thedefined group was derived from coco fatty acids, soybean fatty acids andhydrogenated t-allow fatty acids. Such fatty acids and the correspondingamines which are derived therefrom are well known to the art. Forexample, hydrogenated t-allow acid predominates in 'stea-ric acid andcontains a substantial amount of palmitic acid and very small amounts ofmyristic and oleic acids. Coco fatty acid (distilled) contains about 50%l auric acid and the remainder of the acids range from C to C18,including caprylic, capric, myristic, palmitic, stearic, oleic andlinoleic acids. Soybean fatty acids include mixtures of saturated andunsaturated acids in the C1648 range.

EXAMPLE OF PREPARATION OF A SALT OF 1,2- DISU'BSTITUTED IMID'AZOLINE ANDSUCCI- NAMIC ACID As an example of the preparation of a salt of thisinvention, equirnolar amounts of N-tallow succinamic acid andl-(Z-hydroxyethyl)-2-heptadecenyl imidazoline were mixed in isopropylalcohol solvent with stirring while heating above room temperature for30 minutes. The isopropyl alcohol solvent was then evaporated from theresulting product. The product was 1-(2-hydroxyethyl)-2-heptadecenylimidazolinium N-tallow succinamate.

The above-defined salts are useful as corrosion inhibitors in corrosioninhibiting amounts in hydrocarbon fuels, e.g., in amounts of from about0.0001 to about 0.1 weight percent and preferably in amounts of fromabout 0.0003 to about 0.0015 Weight percent. Concenti'ates of the saltsin hydrocarbon fuels or other suitable solvent, such as xylene, toluene,benzene, phenol, isopropyl alcohol, ethanol, n-butanol, etc., are alsointended. Such concentrates may contain the salt in an amount greaterthan normally used in hydrocarbon fuels as set out above, for example inan amount in the range of 10 to by weight in a suitable solvent. Theprimary function of the R and R groups in the above formula is to impartoil-solubility to the chemical compounds for use in hydrocarbon fuels asadditives and the particular number of carbon atoms in the R and Rgroups is not critical. Other addition agents such as anti-knock agents,anti-ice agents, antioxidants, preignition suppressors, dyes, etc. mayalso be added to the hydrocarbon fuel composition or additiveconcentrate when desired. The salts of this invention, in addition tobeing effective corrosion inhibitors, are also effective rustinhibitors.

The corrosion inhibitors of this invention are effective in both thehydrocarbon (and aqueous phases encountered in the handling and storageof fuels. Hydrocarbon phases are present as the fuel itself and theaqueous phases are produced by condensation and in some cases bycontamination through seepage or from processing of the fuel. Alsopresent in the fuel in many instances are acidic and/or causticsubstances in small amounts resulting from prior treatment of the fuelor a component thereof, e.g., from acid treating and/ or caustictreating. Such acidic and/or caustic materials are corrosive towardmetal parts such as storage tanks, valves, pipelines, tank cars,burners, etc. Other corrosive substances may be formed through oxidativedeterioration of the fuel in the presence of oxygen, particularly if thefuel is stored for substantial periods of time or stored or transportedunder adversely 'high temperature conditions. The corrosive materialsbecome distributed throughout both the hydrocarbon and aqueous phasesand it becomes desirable, if not necessary, to protect against corrosionof metal parts from both phases. The salts of this invention are usefulin giving such protection from corrosion in both phases.

EXAMPLES OF CORROSION INHIBITED HYDROCARBON FUELS As an example of acorrosion inhibited gasoline, Sample A was prepared as identified below.For comparative purposes, Samples B and C were also prepared.

Sample A-A premium grade blended gasoline containing 3 cos. TEL and0.0003 weight percent 1-(2-hydroxyethyl)-2-heptadecenyl imidazoliniumN-tallow succinamate.

Sample BA premium grade blended gasoline containing 3 ccs. TEL and0.0003 weight percent N-t-allow succinamic acid.

Sample CA premium grade blended gasoline containing 3 ccs. TEL and0.0003 weight percent l-(2-hydroxyethyl)-2-heptadecenyl imidazoline.

Sample DA premium grade blended gasoline containing 3 cos. TEL and0.0016 weight percent of a commercial rust and corrosion inhibitor.

The above Samples A-D were subjected to the following corrosion testprocedure: Each sample was placed with an equal volume of an aqueousphase in a test tube and stirred briefly to permit the corrosioninhibiting agent to be distributed between the two phases. Stirring wasthen discontinued. An S-shaped steel test strip, having an electricalterminal at each end of the S was immersed in the oil phase to reachadsorption equilibrium and the electrical resistance was noted as acontrol resistance value. The steel test strip was then lowered into theaqueous phase and after 24 hours the change in electrical resistance wastaken as a measure of corrosion during the 24-hour period. The amount ofcorrosion was then compared with the amount of corrosion obtained in acontrol run without the inhibitor. Results are reported in Table I interms of percent re duction in corrosion compared with the control run.One hundred percent reduction is equivalent to absence of measurablecorrosion. The aqueous phases used consisted of water containing theamounts of corrosive substances listed in Table I below.

TABLE I.-Percent reduction in corrosion Aqueous Phase Containing:

Sample 0.1%

0.1% 0.2% 0.5% 1% NaCl plus NaCl NaOl NaCl NaCl 10- M NaOH PercentPercent Percent Percent Percent A 98 90 90. 5 98.2 B 86. 2 27.6 43. 522. 5 58. 4 C 36. 2 80 25 21.5 39 D 96 63 45 24 66 Sample BA heater oilfraction containing 0.0003 weight percent l-(2-hydroxyethyl)-2-heptadecenyl imidazolinium N-tallow succinamate.

Sample F-A heater oil fraction containing 0.0003 weight percent tallowammonium N-tallow succin amate wherein R" is a tallow group.

The above Samples E and F were subjected to the corrosion test inaccordance with the procedure set out above using 0.1% NaCl plus 10* MNaOH in the aqueous phase. The results were as follows:

Table II Sample: Percent reduction in corrosion rate E 100 F 17 Theabove data of Table II illustrate the superiority of the corrosioninhibitor of the present invention over a related inhibitor of astructure not in accordance with the compositions of this invention. Theone hundred percent reduction in corrosion rate demonstrates perfectcorrosion inhibition under the test conditions.

Although gasoline and heater oil were specifically used in the aboveexamples, the present corrosion inhibitors are useful in any normallyliquid hydrocarbon fuel. For example, the hydrocarbon fuel may be a jet,diesel or other internal combustion engine fuel, a burner fuel or otherheater or furnace fuel, or the like. More specifically, the fuel or fueloil may be a diesel fuel, a gasoline, a jet fuel, a heavy industrialresidual fuel (e.g. bunker C,) a furnace oil, a heater oil fraction,kerosene, a gas oil, etc. The fuel may be a cracked or virgin distillateor mixture thereof. Residual oils are also useable. Advantageously thefuel may boil in the range of about 200 to 750 F. e.g., a distillatefuel oil cut boiling in the 350 to 650 F. range. Other fuels useablewill be readily recognized by those skilled in the art from the abovedescriptions.

It is evident that I have provided new and useful corrosion inhibitorsand hydrocarbon fuels containing the same.

I claim:

1. A fuel composition comprising a major amount of a liquid hydrocarbonfuel and an amount sufficient -to inhibit corrosion of a salt of1,2-disubstituted imidazo- 5 6 line and succinamic acid, said saltcorresponding to the 3. The fuel composition of claim 1 wherein saidhystructural formula: droca'rb-on fuel boils in the gasolinedistillation range.

References Cited by the Examiner H H 2 5 UNITED STATES PATENTS 2,773,87912/1956 Sterlin 44-63 NOH 2,907,646 10/1959 OKelly et al. 44-63 2 52,919,979 1/1960 Martin et al. 4463 OH OH 10 2,944,969 7/1960 Stromberget al. 252392 2 3,060,007 10/1962 Freedman 44-63 h R d R h h h d b dFOREIGN PATENTS w erem Ian are eac open 0 am y rocar on ra 1- Gals of 8to 20 carbon atoms. 832,038 4/1960 Great Britain.

2. The fuel composition of claim 1 wherein said 15 amount of said saltis from 0.0001 to 0.1 weight per- DANIEL WYMAN Primary Exammer' cent. Y.M. HARRIS, Assistant Examiner.

1. A FUEL COMPOSITION COMPRISING A MAJOR AMOUNT OF A LIQUID HYDROCARBONFUEL AND AN AMOUNT SUFFICIENT TO INHIBIT CORROSION OF A SALT OF1,2-DISUBSTITUTED IMIDAZOLINE AND SUCCINAMIC ACID, SAID SALTCORRESPONDING TO THE STRUCTURAL FORMULA: